Recovery of salts from aqueous solutions



May 24, 1938. E. A. SMITH RECOVERY F SALTS FROM 'AQUEOUS SOLUTIONS Filed Jan. 14. 1935 All - lNvsN-roR EL /45 ANTHOA/ CAP/ELEM SMH?! vm/MM,

BY M ATTORNEY Patented May 2,4, 1938 UNiTED STATESy RECOVERY OF SALTS FROM QUEOUS A v SOLUTIONS Elias Anthon Cappelen Smith, New York, N. Y., assigner to Guggenheim Brothers, New York, N. Y., a. co-partnership Application January 14, 1935, serial No. 1,646

` .4 Claims.

'I'liis invention relates to the treatment of waste liquors and has for an object the provision of anA improved method for recovering valuable com- More particularly, Y

ponents from waste liquors.

the invention contemplates the provision of an improved method for treating waste liquors such, for example, as waste pickling liquor and waste liquor produced in themanufacture of paint pig- I ments. A further object of the invention is to l0 provide an improved method of utilizing waste liquors in the production of salts such as ferrousl sulphate, ferrie sulphate and ferrie aluminum sulphate. The invention further contemplates the development of a relatively cheap source of reagents for use in sewage treatment and water purification processes.

Waste liquors from many sourcescontain in solution chemical reagents which have` valuable industrial applicationabut which are wasted because no commercially feasible processes for their recovery are available. For example, impoverished pickling liquors resulting'from the treatment of steel contain considerable quantities of iron'sulphate and some free sulphuric acid, a

representative sample of such liquors containing about 50 grams per liter of iron combined as ferrous sulphate and about 20 grams .per liter of free sulphuric acid al1 in aqueous solution. Dlsposal of large quantities of such liquors is a serious problem and a source of considerable expense and inconvenience to the manufacturer and, in

` some instances, considerable annoyance to the public.

The ferrous sulphate contained in waste pickling liquors, if recoverable, can be employed ad.-

vantageously in many industries. For example. ferrous sulphate can be employed advantageously. either directly or after conversion to ferrie sulphate, in water purification processes and in v4() sewage treatment processes of the chemical pre.-

sanitation through the provision of a relativelyV cheap source of reagents for use in sewage treatj ment processes of the chemicall precipitation type and for use inwater purication processes.

A method or process of my invention involves the treatment of liquor containing ferrous sulphate in aqueous solution to produce ferrous sulphate mono-hydrate. The liquor may be treated to eiect the precipitation of ferrous sulphate monohydratevdirectly therefrom, or the liquor may be treated to effect the precipitation of copperas, and the copperas may be treated to produce ferrolls sulphate mono-hydrate. ,When ferrous sulphate mono-hydrate is produced directly by precipitation from the liquor, the liquor may be concentrated at a temperature below the minimum temperature at which ferrous sulphate monohydrate will 'be precipitated effectively, and the temperature of the concentrated liquor may be raised to effect the precipitation of ferrous sulphatemono-hydrate; ori the liquor may be heated' l' to a temperature above the minimum temperature at which ferrous sulphate mono-hydrate will precipitate eectively to effect concentration of the liquor and precipitation of ferroussulphate mono-hydrate as the liquor becomes sufli- I ciently concentrated. i

The liquor may be concentrated to any sultable degree by the elimination of water prior to the commencement of the precipitating stage through variation of the temperature. In producing ferrous sulphate mono-hydrate by precipitation, l.' prefer to concentrate the liquor at a temperature below '70 C. to a point at which ferrous sulphate will precipitate when the liquor is heated to a temperature above C. and then heat the liquor to a temperature above 70 C. to eiect precipitation. In carrying out this type of operation, the liquor may be maintained at a temperature above 70 C. for any suitable period of time. Temperatures above '70 C. may be employed primarily, or substantially solely, for precipitation purposes, or for the combined purpose of effecting precipitation and effecting further .elimination of water. lIn producing ferrous sulphate mono-hydrate, I may also heat the liquor to a temperature at which ferrous sulphate monoliydrate will precipitate, without effecting any substantial elimination of water at a lower temperature, and maintain it at such a temperature e to eiect elimination of water and precipitation of ferrous sulphate monos-hydrate. Any suitable temperature may be 'employed for the precipitation of ferrous sulphate mono-hydrate', but I prefer to employ a temperature of about '70 C.

to C.- Additional or fresh unconcentrated I liquor in suitable amounts maybe added to the solution is cooled to effect the crystallization of copperas, and the crystallized copperas is separated from the residual liquor which may bev treated further for the recovery of additional iron sulphate. The separated copperas is preferably heated to effect the removal of six vmoleoirles of water of crystallization and produce a product substantially in the form of ferrousl sulphate mono-hydrate (FeSOi-HaO) 'Ihe heating of the copperas is preferably carried out under such conditions as to effect removal of water substantially as fast as it is liberated from the crystal structure.

Removal of water of crystallization fromythe copperas results in the production of' an iron salt more highly concentrated with respect to iron and the sulphate radical and which, consequently, may be shipped more cheaply from itsl point of production to a point of use. The ferrous sulphate mono-hydrate may also be converted more easily than copperas to ferric sulphate when the production of ferric sulphate is desir able. l

When ferrie sulphate is to be produced, the, ferrous sulphate mono-hydrate is treated with a suitable oxidizing agent such as sulphuricacid. Preferably, the ferrous sulphatev mono-hydrate, which is usually in granular or lumpy form, is mixed intimately with sulphuric acid in suitable amount to eect conversion of the ferrous sulphate to ferrlc sulphate to the desired degree.

If the production of ferrie-aluminum sulphate or n uw f: of ferrie sulphate and aluminum 1 is desirable, a relatively cheap aluminum compound capable of reacting with sulphuric acid to form aluminum sulphate may be incorporated inthe iron sulphate product undergoing treatment with sulphuric acid. According to the preferred method of my invention, bauxite is s ed with the ferrous sulphate mono-hydrate, si; lting mixture is subjected to the action of sulphuric acid in a mechanical mixer capable (intimately mining the materials con- G riunite,

uc aniphate or to the mixture ci ferrous ate and compound in an amcunt just oie-nt to provide sulphate radical in the amount required to form slnumsuiphaie with all of the present, when an 7 alumin pound is mixed with the terroirs sulphate, or to convert the ferrous sulphate to ferrie sulphate, or to accomplish both. results, but any desired smaller or larger amount may be added. The aluminum compound may he employed in any suitable amount to estahiish any desired iron-aluminum ratio in the thiol product. A very desirable sewage treatment reagent may be produced by employing the alurniu num compound and sulphuric acid in such amounts as to form a ferrie sulphatelaluminum sulphate product containing iron and aluminum in the proportion of about one part of aluminum to about ten parts of iron, by weight.

Apparatus suitable for carrying out the method or process oi? my invention comprises an evaporating tower through which a solution to be concentrated may be passed downwardly; means for bringing hot gases into direct contact with the solution in the evaporating tower; a' cooling vessel, preferably in the form of a tower through which the hot concentrated solution may be passed downwardly; means for passing a coolingv gas such as air at atmospheric temperature in direct contact with the hot concentrated solution .in the cooling tower; a crystallizing vessel for receiving cooled concentrated solution from the cooling tower and in which crystallization and separation of the copperas (FeSO4-7H2O) takes place; a dryer for the copperas crystals preferably in the form of an inclined rotary tube or kiln through which the copperas crystals may be passed slowly; and means for passing hot gases in direct contact with the copperas crystals during the course of their passage through the dryer. The apparatus may also be provided with means for returning the depleted mother liquor, after separation of the copperas crystals, to the evaporating tower for further treatment. For installations designed to produce ferrie sulphate, or mixtures of iron sulphate and aluminum sulphate, or both, the apparatus may include a mechanical mixer capable of mixing the ferrous sulphate vmono-hydrate intimately with a suitable oxidizing or sulphatizing reagent. The evaporating tower preferably has associated therewith means for circulating the solution undergoing. concentration' continuously, and the means for introducing hot gases into the evaporating tower are preferably so arranged that the hot gases and the solution flow through the tower concurrently.

The invention will be better understood from a consideration of the following description in conjunction with the accompanying drawing illustrating schematically an arrangement of apparatus of my invention which may be employed in carrying out the preferred' method of the invention.

The apparatus illustrated in the drawing comprises an evaporating tower i@ which may be a hollow tower or a tower packed with corrosionresisting material such as checker brick or coke or which may be otherwise designed to` provide large surfaces of contact between solution and A hot gases flowing therethrough. The evaporating tower shown in the drawing is a hollow cylindrical tower provided with a chemical tile lining.

Solution to be concentrated is'introduced into the upper portion of the evaporating tower it through a valved conduit il which communicates with a feed tank l2 and a spray head il. Hot gases are introduced into the upper portion of the evaporating tower near the point of intro duction oi the solution by means oi a conduit i3 which communicates with a source Vof hot gases such as a furnace it. Moisture-ladenhct gases are withdrawn from the lower portion of the evaporating tower through a manifold it sur- Concentrated solution is withdrawn from the lower portion of the evaporating tower through a conduit Ztl having a pump 2i included therein. The conduit 2li communicates with the feed tank i2 and with a branch conduit 22 which communiand distributing the flow of solution passing cates with a' spray-head 23 in the upper portion of a cooling tower 24. The conduits and 2I are provided with suitable valves for controlling portion of the tower through a valved inlet conduit and a distributing header 26.

Moisture-laden air is expelled to the atmosphere through av Valved outlet 2I at the topv of the tower.

relatively deep end portion.

Cooled solution passes from the cooling tower 24 through a conduit 28 to a crystallizing vessel 38. The crystallizing vessel 30 is a trough having an inclined bottom wall and so arranged that, cooled solution from the cooling tower enters a A rotatable screw 3|.is mounted within the crystallizing chamber and so arranged that during rotation it moves crystals formed in the crystallizing vesselfin a direction away from the deep end portion and to the opposite or shallow end portion. Crystals delivered to the shallow end of the crystallizlng vessel by the rotary screw 3| are discharged into a conduit or chute 32 which conducts them d irectly 'to the interior of a rotary. dryer 33. If desired, means such, for example, as a positive drive conveyor or feeder may be provided for conveying crystals from the crystallizing vessel to thedryer. Depleted mother liquor, formed by crystallization of ferrous sulphate from the cooled solution is withdrawn from the deep end portion of the crystallizing vessel by means of a conduit 31% having a pump 35 included therein. The conduit 34 communicates with the feed tank l2 and permits the return of depleted mother-liquor to the evaporating tower for further concentration. A by-pass 38 is provided in the conduit 34 ahead of the pump 35 to permit wasting of the depleted mother liquor, if desired. Suitable valves are provided in the conduits 34 and 35 to permit control of the ow of v depleted mother liquor therethrough. The hot waste gases leaving the cooling tower through the conduit ZI may be passed intive elimination of water from the mass of crystels entering from the crystallizing vessel.` Hot gases are introduced into direct contact with crystals entering the charging end of the dryer by means of a conduit 3'I which communicates with a. suitable source of hot gases such as a fur'- nace 38.- The discharge end portion, of the rotary dryer is surrounded by a hood 4U from which Waste gases are expelled through an outlet 4I and fromy which a dried product is discharged through a chute 42. A by-pass chute 4.3 communicates with the chute 42. Suitable valves are provided in the chutes 42 and 43 to control theflow of dried material to a dried product storage receptacle 44 and to a mixer 45. Suitable storage receptacles 46 and 4I, for reagents such as sulphuric acid and nely divided bauxite, are provided adjacent the mixer. Valved conduits 48 and 50 permit theintroduction of reagents from the storage receptacles 46 and 41 into the mixer.

In employing apparatus of the type illustrated in the drawing for the treatment of waste pickling liquor, the liquor, containing say about 53 grams per liter of iron,and 19 grams per liter of free sulphuric acid is introduced into the feed tank I2 and flows through the conduit II into the upper portion of the evaporating tower I0. Hot gases are introduced from the furnace I4 by means of the conduit I3 into the upper pori tion of the evaporating tower and the liquorand gases iiow downwardly concurrently. The heat contained in the gases and the'mechanical action -of the gases cause evaporation or elimination of water contained in the liquor and the gases and resulting water vapor are withdrawn -by the fan l'I Aand introduced into the stack I8 from where they are discharged into the' atmosphere. Concentrated liquor is withdrawn by means of the pump 2| -and conduit 20 and a portion is passed to the cooler 24 while anotherportion is returned to the feed tank` I2 for redelivery to the evaporating tower.

The process is preferably so controlled that the temperature within the evaporating tower is maintained below the boiling point of water. Hot gases at any suitable temperature may be employed, but, preferably, the feed of liquor and the rate of admission of hot gases to the evaporating tower are so controlled that the concentrated liquor is collected in and discharged from the bottom portion of the tower at a temperature of about 60 C. to 70 C. The return of depleted mother liquor from the cooling tower and concentratedv liquor from the bottom of the evaporating tower are preferably so controlled that the liquor is introduced into the evaporating tower at a temperature of about 40 C. to 50 C.

Concentrated liquor delivered to the cooling tower by means of the conduit 22 is cooled within the cooling tower to a temperature at which, upon standing, copperas will separate therefrom by crystallization. Normally, it is advisable to control concentration of the liquor so that elective separation of copperas by crystallization will take place when the concentrated liquor is cooled through a temperature range of about twenty or thirty centigrade degrees, say from about 60 C. 50r

or 70 C. to about 40 C. or 50 C.

Cooled liquor passes from the lower portion of the cooling tower to the crystallizing vessel in which copperas crystals are formed and separated from the accompanying mother liquor. The depleted mother liquor is preferably delivered by means of the pump 35 and conduit 3@ from the crystallizing vessel to the feed tank I2 from where it enters the evaporating tower with fresh waste pickling liquor and circulating concentrated liquor. eredvby the rotary screw 3l from the crystallizing vessel 30 to the chute 32 which conducts it to the rotary dryer 33. i 38 and copperas delivered to -the dryer pass through the dryer concurrently. During the course of the passage of the copperas through the dryer, all water associated therewith except one molecule of H2O per molecule of ferrous sulphate (FeSO4) .is eliminated, and a dry, granular or lumpy product consisting essentially of ferrous sulphate mono-hydrate (FeSOfi-HaO) is discharged into the chute 42 at the discharge end Crystalline copperas is deliv Hot gases from the furnace with the copperas crystals effect liberation of 76 1factory results by maintaining a temperature of about 110 C. to 120 C. within the dryer and employing a drying period oi' about one hour to one and one-half hours from the time of entry of the copperas to the time of discharge of the ferrous sulphate mono-hydrate (FeSO4-H2O) If ferrous sulphate mono-hydrate'is the desired end product, the material from the dryer may be conducted through thel chute 43 to the storage receptacle M for subsequent use or for packing for shipment. Y

If i'erric sulphate or a mixture of ferric sulphate and aluminum sulphate is desired, the granular product from the dryer may be conducted directly through. the chute 42 to the mixer 45 or the granular material may be first stored in the receptacle M and subsequently conveyed to the mixer.

The granular material from the dryer (consisting essentially of ferrous sulphate mono-hydrate (FeSOi-HzO) is introduced intothe'mixer together with the desired amount of an oxidizing agent such as sulphuric acid, and together with an aluminum compound such as bauxite, if the production of aluminum sulphate is desired. The mixer preferably should be of such construction that its contents maybe heated during the mixing operation. Mixing of the ferrous sulphate and aluminum compound and mixing of the ferrous sulphate or the ferrous sulphate and aluminum compound with the oxidizing agent may be carried out inv separate pieces of apparatus of any suitable type, if desired.

The mixture is maintained in the mixer at a suitable temperature and for a suitable period of time to eiiect the conversion desired. Treatment of a mixture consisting of ferrous sulphate mono-hydrate and a quantity of sulphuric acid containing just sufficient sulphate radical to effect conversion of the ferrous sulphate completely to ferric sulphate for-a period of about one and one-half hours at a temperature of about 200 C. produces satisfactory results. Similar temperatures and periods of treatment produce satisfactory results when the production of aluminum sulphate in the mixture is desired.

I c1aim:- 1. The method of recovering iron sulphate from Waste liquor containing ferrous sulphate in aqueous solution which comprises heating the liquor to a temperature of about 60 C. to 70 C. to eliminate a portion of the water contained therein with the production of a relatively concentrated -solution of ferrous sulphate without precipitating ferrous sulphate mono-hydrate, cooling the concentrated solution thus produced to a temperature of about 40 C. to 50 C. to precipitate copperas in crystalline form, and

-heating the copperas to effect the removal of l ciptate copperas in crystalline form, heating the lcopperas to eiect the removal of water of crystallization. and produce ferrous sulphate mono-hydrate, and subjecting the ferrous sulphate monohydrate to the action of an oxidizing agent to produce ferric sulphate. y

3. The method of recovering iron sulphate from waste liquor containing ferrous sulphate in aqueous solution which comprises passing the solution through a chamberin co-current relation with relatively low temperature combustion gases,v

evaporatingthe thus passing solution at temperatures below 70 C. and forming a relatively concentrated solution without crystallizing ferrous sulphate monohydrate, cooling the solution in a separate chamber and crystallizing copperas therefrom, and converting the copperas into ferrous sulphate monohydrate.

4. The method of recovering iron sulphate from waste liquor containing ferrous sulphate in aqueous solution which comprises passing the solution through a chamber in co-current relation with relatively low temperature waste products of combustion, concentrating the solution by evaporation of water at temperatures below 70 C., thereby preventing the crystallization of ferrous sulphate monohydrate during said evaporal tion, and cooling t-he thus concentrated solution and crystallizing copperas therefrom.

ELIAS ANTHON CAPPELEN SMITH. 

